Dyeing vinyl polymers



Patented Nov. 7, 1944 Karl Heymann,

Meaclville,- Pa., American Viscose Cor Del., a corporation of assignor to poration, Wilmington, Delaware .No Drawing. Application FebruarylS, 1940, Serial No. 319,019

16 Claims.

This invention relates to improvements in methods of dyeing yarns and other shapes comand other shapes comprising vinyl polymers, such as polymers of vinyl'chloride and copolymers. of

vinyl acetate and vinyl chloride. This applications is a continuation in part my application Serial Number 311,109, filed December 2'7, 1939. v

Materials that are not readily permeable to water can not be satisfactorily dyed by the ordinary dyeing procedure usedin dyeing cotton, wool, natural silk and regenerated cellulose. When ordinary methods of dyeing are attempted the dye either doe not penetrate the material and no dyeing is effected or when dyeing is effected the color is not fast and leaches out.

Yarns and other shapes of cellulose acetate which are not readily permeable to water have been dyed when treated with a liquid swelling agent, such as alcohol, acetone or acetic acid. The swelling agent forms or opens pores in the material into which the dye penetrates. There are certain objections to the use of liquid swelling agents. Generally a large amount' of swelling agent is required. Also the swelling agent has a tendency to weaken the yarn or shape.

I have discovered that yarns and other shapes comprising vinyl polymers, such as polymers of vinyl chloride and copolymers of vinyl acetate and vinyl chloride can be successfully dyed with suspension dyestuffs when the. dyeing operation is carried out in the presence of suspensions of certain normally solid organic compounds which have a solubility in polymers of vinyl chloride and copolymersof vinyl acetate and vinyl chloride of 2% or greater under the conditions at which the dyeing is carried out. By the term suspension dyestuffs i meant dyestuffs of the type applicable to cellulose acetate from a dispersion (insoluble anthraquinone and azo dyes) sometimes referred to as dispersol dyes, and the dyestuffs referred to 'hereinaiterintheexamples by-their trade names are of this type. "-Ih'ecom-poun'ds which are re ferred to as assistants include:

Diphenyl Naphthalene I Phenanthrene a-Naphthol fi-Naphthol Thio-fi-naphthol 2.4-dichloro-u-naphthol 2.4-dibromo-a-naphthol 'o-Hydroxydiphenyl 2-chloro-o-phenylphenol 4-chloro-o-phenylphenol o-Cyclohexylphenol ZA-dichloroaniline 2.5-dichlor'oaniline u-Naphthylamine ll-Naphthylamine Phenyl-a-naphthylamine Phenyl-fi-naphthylamine o-Aminodiphenyl p-Aminodiphenyl p-Chlorobenzaldehyde Resorcylaldehydedimethylether p-Dimethylaminobenzaldehyde o-Hydroxyacetophenone Benzophenonep-Hydroxybenzophenone Methyl-B-naphthylketone Camphor- I 8-hydroxyquinoline Benzylsuccinate Methyl-p-bromobenzoate Phenylphthalate fi-Naphthylaoetate Benzhydrol Phenylbenzylcarbinol Fluorenyl alcohol 5. 3-Diphenoxydiethylether p-Methoxydiphenyl Benzyl-a-naphthylether In carrying out my improved method of dyeing a suspension -of asingle assistant or several assistants together may be used. The assistant is, for

example, dissolved in a suitable solvent, such as alcohol, and the assistant in solution and a suitcipitated and dispersed in an acid dye bath. Satisfactory results are also obtained under certain conditions when the phenol solution is added to the dye bath and is not dispersed. The yarn or shape to be dyed is treated with the dye bath containing the assistant in the ordinary manner. This procedure may be followed using various quantities of dyestufi and assistants with differ-' cut dye bath ratios and temperatures of the dye baths depending upon the character of the material being dyed and the type of dyeing that is being carried out. A satisfactory procedure is one in which the dye bath ratio is 1:30 and contains 1.5% suspension dyestuil with 5% or less of assistant based on the weight of the yarn or shape to be dyed. A suitable dye bath temperature is about 50 C. and the duration of the dyeing operation one hour. Other temperatures may also be used.

My invention may also be carried out by applying the assistant from suspension directly to the yarn or shape. When the yarn orshape is thereafter immersed in the dye bath the assistant aids the action of the dye bath on the yarn or shape in the same manner as when it has been added to the dye bath.

Instead of using either of the above methods, I may add the assistant directly to the vinyl polymers before the yarn or shape is formed. The

yarn or shape containing the assistant is treated with the dye bath in the ordinary manner,

The following examples are illustrative of the invention:

Example 1.Yarns comprising copolymers of vinyl acetate and vinyl chloride were dyed in dye baths having a dye bath ratio of 1:30 and containing 1.5% suspension dyestuff and 5% fl-naphthol based on the weight of the yarn. The temperatures of the dye baths were 60 C. and the duration of the dyeing-operation one hour. The dyestuffs that were used were Cibacete Orange 2R Cibacete Scarlet G Acele Violet B Acele Yellow 3G A dye bath was also used with Cibacete Scarlet G 1% and Acele Violet B 1% as the dyestufi.

Example 2.-Yarns comprising copolymers of vinyl acetate and vinyl chloride were dyed in dye baths having a dye bath ratio of 1:30 and containing 1.5% suspension dyestufl' and 5% p-dimethlyamino-benzaldehyde based in the weight of the yarn. The temperatures of the dye baths were 60 C. and the duration of the dyeing operation one hour. The dyestufis there were used were Celliton Red Violet RR Phenacyl Navy Blue PV Phenacyl Red R Celutate Brill. Blue B Cibacete Rubine BS Artisil Direct Yellow 3GP Celliton Fast Pink BA Acele Scarlet G Calconese Orange 3RC Cibacete Violet B Celutate Fast Blue GL Artisil Direct Yellow 3G ex. Phenacyl Red R Example 4.--Yarns comprising copolymers of vinyl acetate and vinyl choride were dyed indye baths having a dye bath ratio of 1:30 and contaming 1. suspension dyestufl and 0-113- .naphthylamine, phenyl-fi-naphthylamine, a-minodiphenyl and :p-aminodiphenyl.

droxydiphenyl based on the weight of the yarn. The temperatures of the dye baths were 60 C. and the duration of the dyeing operation one hour. The dyestuffs that were used were Celliton Pink RF Celliton Red 3? Celliton Orange 3RN Cibacete Yellow 2RN Celliton Fast Yellow GRA Cibacete Yellow 5G Cibacete Brill. Blue BGG Celliton Fast Blue FFRS Celliton Discharge Violet B Cibacete Discharge Violet 5R Camacyl Brill. Green B Phenacyl Red R Cibacete Violet B Artisil Direct Yellow 3 GP ex. cone. Celliton Fast Brown 5RA Example 5.Yarns comprising copolymers of vinyl acetate and vinyl chloride were treated with a bath in a ratio of 1:30 containing 5% o-hydroxydi henyl based on the weight of the yarn at a temperature of 60 C. and for a period of one-half hour. The yarns so treated were then dyed by immersing in dye baths having a dye bath ratio of 1:30 and containing 1.5% suspension dyestufi based on the weight of the yarn. The temperatures of the dye baths were 60 C. and the duration of the dyeing operation one hour. The dyestuffs that were used were Camacyl Brill. Green B Phenacyl Red R Cibacete Violet B Artisii Direct Yellow 3GP ex. conc. Celliton Fast Brown 5RA While preferred assistants and procedures have been shown it is to be understood that changes and variations may be made without departing from the spirit and scope of the invention as defined in the appended claims.

What I claim is:

1. A method of dyeing yarns and other shapes comprising vinyl polymers, comprising the step of treatin the yarn or shapewith an aqueous dye bath containing a suspension dyestuff, in the presence of an organic compound selected from the group consisting of 2.4-dichloroani1ine, 2.5- diohloroaniline, a-naphthylamine, B-naphthylamine, phenyl-a-naphthylamine, phenyi-B- naphthylamine. o-aminodiphenyl and -p-aminodi-phenyl.

2. A method of dyeing yarns and other shapes comprising copolymers of vinyl acetate and vinyl chloride, comprising the step of treating the yarn v or shape with an aqueous dye bath containing a suspension dyestuff, in the presence of an organic compound selected from the group consisting of 2.4-dichloroaniline, 2.5-diohloroaniline, a-naphthylamine, ,B-naphthylamine, phenyl-a- 3. A method of dyeing yarns and other shapes comprising vinyl polymers, comprising the step of treating the yarn or shape with an aqueous dye bath containing a suspension dyestuff and an organic compound selected from the' group consisting of 2.4-dichloroaniline, 2.5-dichloroaniline, a-naphthylamine, fl-naphthylamine, phenyl-a-naphthylamine, phenyl-fl-naphthylamine, o-aminodiphenyl and p-aminodiphenyl disposed in the dye bath.

4. A method'of dyeing yarnsandother shapes comprising copolymers of vinyl acetate and vinyl chloride, comprising the step of treating the yarn or shape with an aqueous dye bath containing a suspension dyestufi and an organic compound selected from the group consisting of 2.4- dichloroaniline, 2.5-dichloroaniline, a-naphthylamine, ,B-naphthylamine, phenyl-a-naphthylamine, phenyl-fi-naphthylamine, o-aminodiphenyl and p-a'minodiphenyl dispersed in the dye bath.

5. A method of dyeing'yarns and other shapes comprising vinyl polymers, comprising the step of treating the yarn or shape with an aqueous dye bath containing a suspension dyestufi in the presence of 2.5-dichloroaniline,

6. Amethod of dyeing yarns and other shapes comprising vinyl polymers, comprising the step of treating the yarn or shape with an aqueous dye bath containing a suspension dyestuff in the presence of p-aminodiphenyl.

7. A method of dyeing yarns and other shapes comprising vinyl polymers, comprising the step 10f treating the yarn or shape with an aqueous dye bath containing a suspension dyestufi in the presence of phenyl-a-naphthylamine.

8. A method of dyeing yarns and other shapes comprising copolymers of vinyl acetate and vinyl chloride, comprising the step of treating the yarn or shape with an aqueous dye bath containing a suspension dyestufi in the presence of 2.5- dlchloroaniline.

9.-A method of dyeing yarns and other shapes comprising copolymers of vinyl acetate'and vinyl chloride, comprising the step of treating the yarn or shape with an aqueous dye bath containing a suspension dyestufi in the presence of p-aminodiphenyl.

chloride, comprising the step of treating the yarn or shape with an aqueous dye oath containing a suspension dyestuff in the phenyLa-naphthylamine.

11. A method of dyeing yarns and other shapes comprising vinyl polymers, comprising the step of treating the yarn or shape with an aqueous dye bath containing a suspension dyestuff and 2.5-dichloroaniline dispersed in the dye bath.

12. A method of dyeing yarns and other shapes comprising vinyl polymers, comprising the step of treating the yarn or shape with an aqueous dye bath containing a suspension dyestufi and p-aminodiphenyl dispersed in the dye bath.

13. A method of dyeing yarns and other shapes comprising vinyl polymers, eomprising the step of treating the yarn or shape with an aqueous dye bath containing a. suspension dyestuff and a suspension dyestufi and p-aminodiphenyl dis- 10. A method of dyeing yarns and other shapes 7 comprising copolymers of vinyl acetate and vinyl persed in the dye bath.

16. A method of dyeing yarns and other shapes comprising copolymers of vinyl acetate and vinyl chloride; comprising the step of treating the yarn or shape with an aqueous dye bath containing a suspension dyestufi and phenyl-a-naphthylamine dispersed in the dye bath.

'KARL HEYMANN.

presence of I 

